Hydrocarbon additive oils



Patented Feb. 6, 1951 HYDROCARBON ADDITIVE OIL Charles Hoffman, Scarsdale, Thomas R. Schweitii-- er, Bellaire, and Mohammad Haider Anwar and Gaston Dalb New York, N. Y., assignors to Ward Baking Company, New York, N. Y,, a

corporation of New York No Drawing. Application July 23, 1947, a Serial No. 763,153 I Our present invention relates to an agent for inhibiting or'preventing the formation of water emulsions and the formation ofgummy substances in hydrocarbon oils, particularly in oils and fuels for internal combustion engines, and for inhibiting corrosion of metal parts by said hydrocarbons, also to improving the penetrating power and film strength of the oils, and also to lubricating oils and motor fuelscontaining an additive agent.

During the use of lubricating oils, such as crank case oil, in the operation of internal combustion engines, gummy or varnish-like substances tend to form by the break down and recombination of the lubricant. Also, water formed by the combustion of the motor fuel tends to become emulis forced by the fuel pump of the engine, and

also tend to clog the filter, causing the oil to bypass it and carry the fine suspended particles, the gummy substances and emulsion into the narrow ducts and passages. Becauseof these actions the oil may fail to penetrate into the spaces between moving parts, particularly if the oil has a low penetrating action, and excessive wear flmay thereby be occasioned. To. guard against such excessive wear a frequent renewal of the oil has been required. I.

Alsoin the motor fuels used for internal combustion engines there is a tendency toward the formation of gummy substances which accumulate in the fuel lines and in the passages of the carbureter which interferes with the proper feed ofthe fuel and the functioning of the engine.

In our present invention we provide an additive agent which inhibits or prevents the formation of water emulsions and of gummy or varnishilike materials in lubricating oils and motor; fuels and which also improves the penetrating power and the strength of film of the lubricant.

Our improved agent also has a detergent action which tends to keep the crank case clean and to improve the filtering of the .oil in the oil filter. It also prevents corrosion of the oil ducts and of thebearings or other moving parts and avoids 12 Claims. (Cl. 252-325) 2' I excessive wear of those-partsby the formation; of suspended particles in the oil or lubricant. The addition agent of our invention comprises the reaction product of an anionic surface active organic phosphorus compound of the general formula Na5R5(P3O1o)2, in which R stands for a hy-..- drocarbon chain having from 6 to 10 hydrocarf hens and with or without side chains, with an organic sulphonate or sulphate of a long chain hydrocarbon or alkyl compound. Any suitable; salt of the sulphateor-sulphonate may be 'em-: ployed, such as sodium salt. During the reaction some insoluble material separates from the re-i action product and thesulphate or sulphonate combines with the complex phosphatecompound; An example of an organic sulphonate is the sodium salt of a sulphonated dioctyl succinic ester or other double-ester of a sulphonated succinic ac d or dibasic acid; r Examples ,ofa hydrocarbon sulphate arez"; g g (1) '7 ethyl-2 methyl-4 undecanol sodiumsuh phate I. Y mmcn'winscimcncmcmcnm SOJNE 2) 3-9 diethyl-6 tridecanolsodium sulphate.

C H CH(C2H5)CilLCHC EhCHQ' Hm 5 solNa' (3) 2-8 diethyl-duodecanol sodium sulphate.

ciH1oH(c236)ciHicnczfi omoiHm The sodium alkyl phosphateof the above type is water soluble but insoluble in oil, whereas the hydrocarbon sulphates and sulphonates are oil miscible" and to some extent 'water'soluble. When .1 sodium alkyl, phosphate is-heated and reacted wi'th...an a yll ulph e r su phonatenf the. above. group itbecomes. oil solubleand may be dissolved in hydrocarbon :oil. f H Examplesfof the reaction of .the phosphate and sulphate compounds arenas followsz. .1 6 parts or; sodium salt-of the-dioctyl ester of. sulphonated succinigc'acid and 4-parts of aphos phate which has a chain of G-carbon atoms having an ethylsidechain, the compound having the formula: 5'.-

H' HQH H1 11,0-0-0-0-0-0H3);

Jam."

. a 1o)2 5 are mixed with 10 parts of water-by wei pp aise: e9. Pitts. elical! nd i heated-until the mixture thickens and most of or centrifuged to separate and remove any inorganic salts that may be formed. and to get. a.

clear solution.

Example .2v

Similarly, 4 parts of the above phosphate compound and 5 parts of one of the alkyl secondary sulphates mentioned above are heated with 10 parts of water and then heated as above. with: hydrocarbon oils to a final temperature of 150 C. (300 F.), and filtered or centrifuged. It is not necessary to hold the temperature to 150 C. during or after the reaction as the reaction products are stable at temperature considerably above this temperature.

An excess of the sulphates orsulponates may be used over and above the above. proportions and will remain merely as anexcess. If an excess of the phosphate be'used a gummy prodnot will be formed. Any alkyl sulphate or sul phonate may be combined with aphosphorus compound providing the length of the alkyl chain is sufficient to make the resulting compound oil soluble. A chain of from 11 to 18 carbon atoms may be used, but preferably one having from 11 to-13 carbon atoms.

This solution containing about 20% of the reaction products in oil is used in the ratio of ounce per' quart of oil to provide the oil with about 023 by weight of the combined additive. The amount:v used to inhibit formation of gum in gasoline is about 0.05 on the basis of com bined additive or 0.25 of; the solution of additfi ein oil.

It will be understood that the amount of additive may'vary Somewhat from. the; percentages given above, which are. given by way of example to indicate the small quantities of the additive required to inhibit gum formation and" to prevent emulsification. of oil and water and to inhibit corrosion of .the metal parts being lubricated.

An example of the effect of the additive on gum formation as shown, by the copper dish method, is indicated by the following table of tests on a number of representative gasolines. The amount of additive used was 0.05% of the pure-additive-or gram per liter: I

" Gum Within-1t.v Gum- With I Gasoline. Samples Miditive Additive 1 5.0 mg. per 100 cc' Z mg. per 1'00 cc. 2 23.0 m 2.0 mg.

516 m 23 mg.

4'. 42.0 mg j1.4 mg.

5 141.8 m 6 3 mg.

6 2 2 ma. 2 6 mg.

1., 106.6 mg .8 mg.

; (glean; and free f-rom deposits. The all contain:- ;.;lnggtheadditive filters more freely and has an increased capacity to penetrate the narrow passages of the motor and to remain therein.

What we claim is:

1. The reaction product formed by heating above about. C. until the product is oil soluble, four parts by weight of sodium penta alkyl tripoly phosphate in which the alkyl radical has a chain of from 6 to 10 carbon atoms and at. leastfive parts by weight of a member of the class consisting of the sodium sulphonates of dibasic saturated alkyl acid esters and of secondary alkyl sulphates having a carbon chain of from 11 to 18. carbon atoms.

2. The reaction product formed by heating above about 130 C. until the product is oil soluble, four parts by weight of sodium penta ethyl hexyl tripoly phosphate and at least five parts by weight of a member of the class consisting of the sodium sulphonates of saturated alkyl dibasic acid esters and of secondary alkyl sulphates having a carbon chain of from 11 to 18 carbon atoms.

3. The reaction product formed by heating above about 130 C. until the product is oil soluble, four parts by weight of sodium penta octyl tripoly phosphate and at least fiveparts. by weight of a member of the class consisting of the sodium sulphonates of saturated alkyl. dibasic acid esters and of secondary alkyl. sodium sulphates having a carbon chain of. from 11 to 18 carbon atoms.

4. The reaction product formed by heating above about 130 C. until the product is oil soluble, four parts by weight of sodium pentav alkyl tripoly'phosphate in which the alkyl radical has a chain of from 6 to 10 carbon atoms= and at least five parts by weight of the sodium salt of sulphonated dialkyl succinic ester.

5. The reaction product formed by heating above about 130 C. until the product is oil soluble, four partsby weight of sodium penta alkyl tripoly phosphate in which the alkyl radical has a chain of from 6 to 10 carbon atoms and at.

. leastfive parts by weight of the sodium. salt of sulphonated dioctyl succinic ester.

6. The reaction product formed by heating above about 130 C. until the product is oil soluE ble, four parts by Weight of sodium penta octyl tripoly phosphate and at least five parts by weight of dioctyl succinic. ester sodium sulphonate.

7. A hydrocarbon oil containing between 0.05% and 1.0% of the. reaction product formed by heating above about 130 C. until oil soluble four parts by weight of sodium penta alkyl tripoly phosphate in which the alkyl radical has a chain or. from 61 to 10 carbon atoms and at least five parts by weight of a member. of. the class. con; sisting, of the sodium sulphonates of saturated alkyl dibasic acid esters and of secondary alkyl sodium sulphates having a carbon chain of from 11 to 18 carbon atoms.

8. A- hydrocarbon oil containing from 0.05% to 1.0% of a reaction product formed. by heating above about 130 C. untiloili soluble four parts by weight of; a sodium penta alkyl tripoly phosphate inv which the alkyl radical has a chain of fi'om 6 to 10 carbon atoms and at leastfive parts by weight of sodium sulphonate of dioctyl suc ci-nic ester.

9. A hydrocarbon oil containing from 0.05% to 1.0% of the reaction product formed by heating above about 1'30 6. until oil soluble. four parts by weightof a; sodium'penta octyl tripoly phos- 5 phate and at least five parts by weight of a sodium sulphonate of dioctyl succinic ester.

10. A process of making a corrosion and emulsion .inhibiting additive for hydrocarbon oils which comprises heating to at least 130 C. until oil soluble, four parts by weight of sodium penta alkyl tripoly phosphate in which the alkyl radical has a chain of from 6 to 10 carbon atoms with at least five parts by weight of a member of the class consisting of the sodium sulphonates of saturated alkyl dibasic acid esters and of secondary alkyl sodium sulphates having a carbon chain of from 11 to 18 carbon atoms.

11. A process of making a corrosion and emulsion inhibiting additive for hydrocarbon oils which comprises heating to at least 130 C. until oil soluble a solution of four parts by weight of a penta alkyl tripoly sodium phosphate in which the alkyl radical has a chain of from 6 to 10 carbon atoms, and at least five parts by weight of a member of the class consisting of the secondary alkyl sodium sulphates having a chain of from 11 to 18 carbon atoms in ten parts by weight of water until the solution thickens, addin twenty parts by weight of a light hydrocarbon oil and heating until the water is evaporated.

12. The process of making a corrosion and emulsion inhibiting additive for hydrocarbon oils which comprises heating to above about 130 C. until oil soluble a solution of four parts by weight of sodium penta octyl tripoly phosphate and at least five parts by weight of a sodium sulphonate of "dioctyl succinic ester in ten parts by weight of water until the solution thickens, adding twenty parts by weight of a light hydrocarbon oil, heating until the water is evaporated, thereafter addingabout twenty parts by weight of a solvent hydrocarbon oil and heatin said mixture to a temperature of at least about 150 C.

CHARLES HOFFMAN.

THOMAS R. SCHWEITZER. MOHAMMAD HAIDER ANWAR. GASTON DALBY.

REFERENCES CITED The following references are'of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,119,523 Butz June 7, 1938 2,294,526 Waugh Sept. 1, 1942 2,367,470 Neely Jan. 6, 1945 2,369,632 Cook et a1. Feb. 13, 1945 2,417,876 Lewis et a1 Mar. 25, 1947 2,418,422 Palmer Apr. 1, 1947 OTHER REFERENCES Adler et al.: Chemical Industries, vol. 51, No. 4, Oct. 1942, page 520. 

7. A HYDROCARBON OIL CONTAINING BETWEEN 0.05% AND 1.0% OF THE REACTION PRODUCT FORMED BY HEATING ABOVE ABOUT 130* C. UNTIL OIL SOLUBLE FOUR PARTS BY WEIGHT OF SODIUM PENTA ALKYL TRIPOLY PHOSPHATE IN WHICH THE ALKYL RADICAL HAS A CHAIN OF FROM 6 TO 10 CARBON ATOMS AND AT LEAST FIVE PARTS BY WEIGHT OF A MEMBER OF THE CLASS CONSISTING OF THE SODIUM SULPHONATES OF SATURATED ALKYL DIBASIC ACID ESTERS AND OF SECONDARY ALKYL SODIUM SULPHATES HAVING A CARBON CHAIN OF FROM 11 TO 18 CARBON ATOMS. 